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Controlled nucleophilic activation of different sites in [Mo 2Cp2L2(μ-SMe)2(μ-L′)] + cations (L = ButNC, xylNC, CO; L′ = SMe or PPh2)
- Source :
- Journal of Organometallic Chemistry, Journal of Organometallic Chemistry, Elsevier, 2005, 690 (21-22), pp.4583-4601. 〈10.1016/j.jorganchem.2005.07.034〉, Journal of Organometallic Chemistry, 2005, 690 (21-22), pp.4583-4601. ⟨10.1016/j.jorganchem.2005.07.034⟩, Journal of Organometallic Chemistry, Elsevier, 2005, 690 (21-22), pp.4583-4601. ⟨10.1016/j.jorganchem.2005.07.034⟩
- Publication Year :
- 2005
- Publisher :
- HAL CCSD, 2005.
-
Abstract
- The thiolato-bridged binuclear molybdenum complexes [Mo 2 Cp 2 L 2 (μ-SMe) 2 (μ-L′)]Y (Cp = η 5 -C 5 H 5 ; L′ = SMe, L = Bu t NC ( 1a ), xylNC ( 1b ) or CO ( 3 ); L′ = PPh 2 , L = Bu t NC ( 16 ); Y = BF 4 , Cl) react with the anionic reagents NaBH 4 , NaBD 4 , LiR (R = Me, Bu n ), R′MgCl (R′ = Me, Pr i , Bu n or Ph). The products are unsubstituted ( 5 , 7 ) or substituted ( 8 – 12 ) η 4 -cyclopentadiene derivatives, [Mo 2 (η 5 -C 5 H 5 )(η 4 -C 5 H 5 R)L 2 (μ-SMe) 3 ] (L = xylNC, CO), or μ-formimidoyl dinuclear products, [Mo 2 Cp 2 L 2 (μ-SMe) 2 (μ-L′)(μ-CHNR)] (L′ = SMe, L = Bu t NC ( 4 ) or xylNC ( 6 ); L′ = PPh 2 , L = Bu t NC ( 17 )). Since the reduced dinuclear species [Mo 2 Cp 2 (CO) 2 (μ-SMe) 2 ] and the related oxo-compound [Mo 2 Cp 2 (CO)(O)(μ-SMe) 2 ] are sometimes isolated as minor products, the anionic reagent can play a secondary role as a reductant in these reactions in addition to its main role as a nucleophile. The electronic properties of the donor carbon atoms of the cyclopentadienyl rings and of the terminal ligands L, together with the nature of the anionic reagent, are the dominant factors controlling selective formation of 4 – 12 and 17 . Tetrafluoroboric acid reacts with the substituted cyclopentadiene derivatives 9 , 11 and 12 to form new functionalised cyclopentadienyl derivatives, [Mo 2 (η 5 -C 5 H 5 )(η 5 -C 5 H 4 R)(CO) 2 (μ-SMe) 3 ](BF 4 ) (R = Me ( 13) , Bu n ( 14 ) or Ph ( 15 )). New complexes have been characterised by spectroscopic and chemical methods, supplemented for 5 , 6 and 12 by X-ray diffraction studies at 100 K.
- Subjects :
- Cyclopentadiene
Stereochemistry
X ray diffraction
chemistry.chemical_element
Molybdenum compounds
Crystal structure
010402 general chemistry
Spectroscopic analysis
01 natural sciences
Biochemistry
Medicinal chemistry
[ CHIM ] Chemical Sciences
Negative ions
Inorganic Chemistry
chemistry.chemical_compound
Cyclopentadienyl complex
Nucleophile
Materials Chemistry
[CHIM]Chemical Sciences
Physical and Theoretical Chemistry
Cyclopentadienyl
Isocyanide liagand
Reaction kinetics
Electronic properties
010405 organic chemistry
Chemistry
Activation analysis
Nucleophilic activation
Organic Chemistry
Organometallics
0104 chemical sciences
3. Good health
Dimolybdenum complexes
Boron compounds
Molybdenum
Reagent
Complexation
Formyl ligand
Carbonyl ligand
Thiolato-bridged complexes
Subjects
Details
- Language :
- English
- ISSN :
- 0022328X
- Database :
- OpenAIRE
- Journal :
- Journal of Organometallic Chemistry, Journal of Organometallic Chemistry, Elsevier, 2005, 690 (21-22), pp.4583-4601. 〈10.1016/j.jorganchem.2005.07.034〉, Journal of Organometallic Chemistry, 2005, 690 (21-22), pp.4583-4601. ⟨10.1016/j.jorganchem.2005.07.034⟩, Journal of Organometallic Chemistry, Elsevier, 2005, 690 (21-22), pp.4583-4601. ⟨10.1016/j.jorganchem.2005.07.034⟩
- Accession number :
- edsair.doi.dedup.....00592a53fe6b82c1d4e8ea507d0540ec